Reactive azo dyes derived from 3-(4-aminophenyl)-5-chloro-1, 2, 4-thiodiazole as the diazo component



United States Patent Oifice 3,398,134 Patented Aug. 20, 1968 7 Claims.(of. 260-157) ABSTRACT OF THE DISCLOSURE Water-soluble reactive azo dyesof the formula where A is the radical of the coupling component of theformulae in which R is hydrogen, amino, acetylamino, benzoylamino,fi-chloropropionylamino or phenylureido, R is hydrogen, 4-sulfophenylazoor 4-nitro-2-sulfophenylazo, R is hydrogen, fumarylamino, succinylaminoor fi-sulfopropionylamino, R is hydrogen, chloro or methyl, R ishydrogen or chloro, R is methyl or carboxy, z is hydroxyl or amino, n isone of the integers 1 or 2 with the proviso that the sulfo groups areattached formulae a and b in the 3, 4, 5, 6, 7 or 8 positions andfurther that only one of R R and R can be other than hydrogen. Thedyestuffs dye cellulosic fibers with high color strength and excellentdyebath exhaustion.

The invention relates to new reactive azo dyes which are derived fromthe diazo component of the formula A great number of reactive azo dyeshave already been described in the patent literature and are in use allover the world. Reactive dyes for dyeing cotton have found universalacceptance in the dyeing industry inasmuch as this class of dyes offersmany advantages over the very fast but expensive vat dyes and theinexpensive but poorly fast direct dyes. Reactive dyes can be producedat a moderate price and yield dyeings of high wash fastness, good lightfastness and bright shades. For this reason, they are often preferred tothe vat dyes because of their brighter shades and lower price and to thedirect dyes because of their high wash fastness. All reactive dyes,whatever reactive group they may have, still have one shortcoming, i.e.only a certain percentgae, as a rule somewhat more than 50 percent ofthe dye, is

chemically attached to the fiber. The rest of the amount of the dyeinitially used is hydrolyzed to a non-reactive form by the water of thealkaline dyeing liquor. In the soaping step of the dyeing procedure thehydrolyzed dye is removed and is lost by draining off. Therefore, thehydrolysis which competes with the reaction of the dyes with the fibersshould be as low as possible, in order that a high yield of fixation isobtained and as large a percentage as possible goes on the fibers thusyielding deep shades. Another possibility of obtaining deeper shades byemploying the same or even smaller amounts of dyes than usual resides inseeking dyes which have either greater color strength, i.e. molarextinction, or greater affinity to the fiber.

Among the numerous reactive groups suggested in the literature so farfor the production of reactive dyes there have also been describedchlorothiazoles and chlorothiodiazoles. Dyes having these groups arevery valuable dyestuffs although they also have the above mentionedshortcomings. It was therefore an object of this invention to providedyes which go on cellulosic fibers and are fixed in a high rate whereashydrolysis is relatively low. A further object of the invention was toprovide reactive dyes which have an excellent color strength, i.e. whichhave a high molar extinction. Thus dyeing in deep shades can be obtainedby employnig smaller amounts of dyes than usual. These objects of theinvention are achieved by dyes of the formula where A is a radical ofthe coupling component of the formulae R2 Z (S 3 )n (3 3 Ra Tq-Rc O N/in which R represents hydrogen, amino, acetylamino, benzoylamino,B-chloropropionylamino or phenylureido; R represents hydrogen,4-sulfophenylazo, 4-nitro-2-sulfophenylazo or4-acryloylamino-3-sulfophenylazo; R represents hydrogen, fumarylamino,succinylamino or fi-sulfopropionlyamino; R represents hydrogen, chloroor methyl; R represents hydrogen or chloro; R represents methyl orcarboxy, Z represents hydroxy or amino; and n represents one of theintegers 1 and 2 with the proviso that the sulfo groups are attached tothe components of Formulae a and b in the 3, 4, 5, 6, 7, or 8 positionsand with the further proviso that only one radical of R R and R can beother than hydrogen.

As already mentioned above, reactive dyes containing a chlorothiazol orchlorothiodiazole reactive group have already been described in theliterature, namely in Belgian patent specification 630,929. Amongnumerous amines having these reactive groups there is also mentionedm-aminophenyl-chlorothiodiazole. All the compounds disclosed in the saidpatent already have excellent tinctorial properties. It was thereforequite unexpected that the specific diazo component as used according tothe invention would lead to dyes with still further improved tinctorialproperties. In fact the properties of the new dyes are so outstandingthat dyeings prepared with these dyes, especially by the so calledexhaustion method, exceed dyeings prepared with the same amounts of thecorresponding dyes of the meta-compound by nearly twice the depth ofcolor. This is due to a greater molar extinction of the dyes of theinvention and a higher affinity to cellulosic fibers, i.e. the dyebathis better exhausted.

Amines having the formula I may be obtained for example from thecorresponding nitro compounds by reand The following examples willfurther illustrate this invention. The parts and percentages specifiedin the examduction of the nitro group, advantageously by hydropics areby weight unless otherwise indicated. Parts by genation in a solvent inthe presence of hydrogenation volume bear the same relation to parts byweight as the catalysts, preferably Raney nickel. The correspondingliter to the kilogram. nitro compounds are obtainable for example byreaction a of p-nitrobenzamidines with perchloromethylmercaptan EXAMPLE1 by the method described in Chemische Berichte, 90 (1957) 182.

Diazotization and coupling are carried out by con- Parts of "9P Y 'Lventio l th d azole having a melting point of 148 to 150 C. (obtain-Examples of coupling Components A-H in whi h A able from4-nitrobenzamidine and perchloromethylmerhas the above meaning areinaphthol sulfonic acids, captan, for the method see Chem. Ber. 90 (1957)182) aminonaphthol sulfonic acids, acylaminonaphthol sulis reduced withhydrogen in 500 parts by volume of difonic acids, S-pyrazolone sulfonicacids and also hydroxyoxane using Raney nickel as catalyst. After thecalcul SulfonlC aclds Speclfic eXampleS am! lated amount of hydrogen hasbeen absorbed, the catachloro 5 P Y 3 methylpyfalolom lyst is filtered01f and the amine obtained is precipitated 1 (2,5 'dlchloro 4sulfophenyl) 3 methylpyra' by adding 1500 parts of icewater. Theprecipitate is suc- Zolone 1 (2 methyl 4 Sulfophenyl) tion filtered anddried at subatmospheric pressure at 50 methylpyrazolone 1 (3Sulfophenyl) C. 17.5 parts of3-(4-aminophenyl)-5-chloro-1,2,4-thiomethylpyrazolone 1 (4 ulfophenyndiazole is obtained; after having been recrystallized frommethylpyrazolone 1 (2,5 dlsulfophenyl) a mixture of alcohol and water(1:1) it melts at 109 methylpyrazolone (5), 1 (4 sulfophenyl) 3 carto Cb9xypyrllzolon? 1 hydroxynaphthalene 21.2 parts of the3-(4-aminophenyl)5-chloro-1,2,4- dlsulfomc acid, 1 hydroxynaphthalene3,8 disulthiodlazole thus obtained 15 dissolved in 220 parts of fonrcacid, 2 hydroxynaphthalene 6,8-drsulfonic glacial acetic acid. Then 25parts by volume of 36% acid, 2 aminonaphthalene 5,7 dlsulfomc acid, 1-

0 hydrochloric acid is added and the amine 1s diazotizedhydroxynaphthalene 4,6 disulfonlc acid, 1 hyt C 7 f 1 d droxynaphthalene47 disulfonic acid 1 acetyli o parts 0 so mm n e lssio in 200 parts byvolume of water. The diazo solution 18 amino 8 hydroxynaphthalene 3,6disulfomc acid,

added slowly to a neutral solution of 23 parts of l-naph- 1benzoylarnino 8 hydroxynaphthalene 3,6 disulv f thol-4-sulfon1c acid in300 parts by volume of water, the

onic acid, 1 acetylamino 8 hydroxynaphthalene- 4,) reaction of themixture being kept at pH 4 to 5 by gradu- 4,6 disulfonic acid, 1benzoylammo 8 hydroxyna hthalene 4 6 disulfonic acid or the com ounds a1addition at the same time of 30 parts of sodium hyh 5. the for p drogencarbonate. The deposited dye is suction filtered a mg m and dried. Itdyes cotton bright red shades by the con- OH NH: ventional methods forreactive dyes.

l l Dyes obtained from the diazo component3-(4-aminophenyl)-5-chl0ro1,2,4-thi0diazole and the coupling componentsindicated in the following table are obtained in o the same way and givethe shades indicated on cotton:

Ex. Coupling component Shade on No. cotton 21-(2-chloro-6-sulfcphenyl)-3-methyl-pyrazolone-(5) Yellow. 31(2,5-dichloro-4-sulfophenyl) -3-methylpyrazolone-(5) D0. 41-(2methyl-4-su1fophyenyl) -3-m ethylp yrazolone-(5) D 0. 51-(3-su1fopheny1) -3-methylpyrazolone-(5) Do. 61-(4-sultopheuyl)-3-methylpyrazo1one'(5) Do. 71-(2,5-disu1tophenyl)-3methyl-pyrazolone-(5). .Do. 81-(4-sulfony1)-3-carboxypyrazolone-(5) Do. 91-hydroxynaphthalene-3,6-disulfonic acid Scarlet. 10-l-hydroxynaphthalenc-3,8-disulfonic acid Do. 11..2-hydroxynaphtha1ene'6,8-disulfonic acid Orange.

2-aminonaphthalene-5,7-disul1onic acid.

1-hydroxynaphthalene-4,6-disulionic acid l-hydroxynaphthalene- Red.

4,7-disulfonic acld.

1 acetylamino-8-hydroxynaphthalene-3,fi-disultonic acid D0.1-benzoy1amino-S-hydrcxynaphthalene-3,6-disu1fonie acid.1-acety1amino-8-hydroxynaphthaIene-4,G-disulfonic acid Do. 171-benzoylamino-S-hydroxynaphthalcue-4,6-disulfouic acid Do.

0 H NHr N avy blue.

Ex. Coupling component Shade on No. cotton ()H 1:11-12 19. N=NN0 Do. IHO S SO H SOQH I 20 Scarlet;

H038 )-NHCOCH=CHCOOH HO3S NHCOCH2OH1OOOH H0 8 \/NHCO CHzCHzSOd-I (|)HIIIHCOCHzCHzCl 23 Red.

Hons SO3H CI H IFHCONH- 24 w Do.

H0 8 SO H (1)11 111E; SO H 25 N=N- -NHCOCH=CH Navy blue. HO3S /SOaH Weclaim:

1. A dye of the formula where A is the radical of a coupling componentselected from the group consisting of the formulae OH R1 (S K )n inwhich R represents a member selected from the group consisting ofhydrogen, amino, acetylamino, benzoylamino, j3-chloropropi0nylamino and)phenylureido', R

represents a member selected from the group consisting of hydrogen,4-sulfophenylazo and 4-nitro-2-sulfophenyl- 2120, R represents a memberselected from the group consisting of hydrogen, fumarylamino,succinylamino and fl-sulfopropionylamino, R represents a member selectedfrom the group consisting of hydrogen, chloro and methyl, R representsamember selected from the group consisting of hydrogen and chloro, Rrepresents a member selected from the group consisting of methyl andcarboxy, Z represents a member selected from the group consisting ofhydroXyl and amino, and n represents one of the integers 1 and 2 withthe proviso that sulfo groups are attached to the components of Formulaea and b in the 3, 4, 5, 6, 7, or 8 position and with the further provisothat only one radical of R R and R can be other than hydrogen.

2. The dye of the formula SOaH 7 3. The dye of the formula 4. The dye ofthe formula 8 5. The dye of the formula 7. The dye of the formulaReferences Cited FOREIGN PATENTS 1,359,435 3/1964 France.

FLOYD D. HIGEL, Primary Examiner.

